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3-Amino-1-(4-fluorophenyl)-8-methoxy-1

H

-benzo[

f

]chromene-2-carbonitrile

Ahmed M. El-Agrody,a,bMohamed A. Al-Omar,c,d Abd El-Galil E. Amr,d,e‡ Seik Weng Ngf,gand Edward R. T. Tiekinkf*

aChemistry Department, Faculty of Science, King Khalid University, Abha 61413, PO Box 9004, Saudi Arabia,bChemistry Department, Faculty of Science, Al-Azhar University, Nasr City, Cairo, 11884, Egypt,cPharmaceutical Chemistry Department, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia,dDrug Exploration & Development Chair (DEDC), College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia,eApplied Organic Chemistry Department, National Research Center, Dokki 12622, Cairo, Egypt,fDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, andgChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia Correspondence e-mail: [email protected]

Received 25 February 2013; accepted 25 February 2013

Key indicators: single-crystal X-ray study;T= 295 K; mean(C–C) = 0.003 A˚; Rfactor = 0.049;wRfactor = 0.138; data-to-parameter ratio = 16.0.

The title compound, C21H15FN2O2, features an approximately

planar 1H-benzo[f]chromene fused-ring system (r.m.s. devia-tion for the 14 non-H atoms = 0.052 A˚ ), with the fluoro-benzene ring being almost perpendicular to this [dihedral angle = 85.30 (7)]. The furan ring has a flattened half-chair

conformation, with the methine C atom deviating by 0.132 (2) A˚ from the plane of the remaining atoms (r.m.s. deviation = 0.0107 A˚ ). In the crystal, inversion dimers are formedviapairs of amine–cyano N—H N hydrogen bonds. The dimers are connected into a three-dimensional architec-ture by C—H N(cyano), C—H and–[intercentroid distance = 3.6671 (10) A˚ ] interactions.

Related literature

For background and various applications of benzo- and naphthopyran- derivatives, see: Bonsignore et al. (1993); Hafez et al. (1987). For background to the chemistry and biological activity of 4H-pyran derivatives, see: El-Agrodyet al.(2011); Sabryet al.(2011). For related structures, see: Wang

et al.(2008); Shekharet al.(2012); Amret al.(2013).

Experimental

Crystal data

C21H15FN2O2

Mr= 346.35 Triclinic,P1

a= 8.9672 (7) A˚

b= 10.4365 (8) A˚

c= 10.9058 (8) A˚

= 103.063 (7)

= 106.859 (7)

= 111.399 (8)

V= 844.01 (11) A˚3

Z= 2

MoKradiation

= 0.10 mm1

T= 295 K

0.300.200.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)

Tmin= 0.722,Tmax= 1.000

7109 measured reflections 3902 independent reflections 2716 reflections withI> 2(I)

Rint= 0.023

Refinement

R[F2> 2(F2)] = 0.049

wR(F2) = 0.138

S= 1.05 3902 reflections 244 parameters

H atoms treated by a mixture of independent and constrained refinement

max= 0.20 e A˚ 3

[image:1.610.312.565.522.579.2]

min=0.16 e A˚ 3

Table 1

Hydrogen-bond geometry (A˚ ,).

Cg1 is the centroid of the C1–C4,C9,C10 ring.

D—H A D—H H A D A D—H A

N1—H1 N2i

0.89 (2) 2.16 (2) 3.043 (2) 170.0 (18) C19—H19 N2ii

0.93 2.51 3.259 (3) 138

C11—H11 Cg1iii

0.98 2.90 3.7084 (17) 141 C14—H14C Cg1iv

0.96 2.92 3.772 (3) 148

Symmetry codes: (i) xþ2;yþ1;zþ2; (ii) xþ1;yþ1;zþ2; (iii)

xþ1;yþ1;zþ1; (iv)xþ1;yþ2;zþ1.

Data collection: CrysAlis PRO(Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97(Sheldrick, 2008); program(s) used to refine structure:SHELXL97(Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Bran-denburg, 2006); software used to prepare material for publication: publCIF(Westrip, 2010).

The authors extend their appreciation to the Deanship of Scientific Research at King Saud University for funding this work through the research group project No. RGP-VPP-099. We also thank the Ministry of Higher Education (Malaysia)

organic compounds

o476

El-Agrodyet al. doi:10.1107/S160053681300545X Acta Cryst.(2013). E69, o476–o477

Acta Crystallographica Section E Structure Reports

Online

ISSN 1600-5368

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Research scheme (UM.C/HIR-MOHE/SC/12).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB7047).

References

Agilent (2011).CrysAlis PRO. Agilent Technologies, Yarnton, England. Amr, A.-G. E., El-Agrody, A. M., Al-Omar, M. A., Ng, S. W. & Tiekink,

E. R. T. (2013).Acta Cryst.E69, o478–o479.

Bonsignore, L., Loy, G., Secci, D. & Calignano, A. (1993).Eur. J. Med. Chem.

28, 517–520.

El-Agrody, A. M., Sabry, N. M. & Motlaq, S. S. (2011).J. Chem. Res.35, 77–83. Farrugia, L. J. (2012).J. Appl. Cryst.45, 849–854.

Hafez, E. A. A., Elnagdi, M. H., Elagamey, A. G. A. & El-Taweel, F. M. A. A. (1987).Heterocycles,26, 903–907.

Sabry, N. M., Mohamed, H. M., Khattab, E. S. A. E. H., Motlaq, S. S. & El-Agrody, A. M. (2011).Eur. J. Med. Chem.46, 765–772.

Shekhar, A. C., Kumar, A. R., Sathaiah, G., Raju, K., Rao, P. S., Sridhar, M., Narsaiah, B., Srinivas, P. V. S. S. & Sridhar, B. (2012).Helv. Chim. Acta,95, 502–508.

Sheldrick, G. M. (2008).Acta Cryst.A64, 112–122.

Wang, X.-S., Yang, G.-S. & Zhao, G. (2008).Tetrahedron Asymmetry,19, 709– 714.

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supporting information

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Acta Cryst. (2013). E69, o476–o477

supporting information

Acta Cryst. (2013). E69, o476–o477 [doi:10.1107/S160053681300545X]

3-Amino-1-(4-fluorophenyl)-8-methoxy-1

H

-benzo[

f

]chromene-2-carbonitrile

Ahmed M. El-Agrody, Mohamed A. Al-Omar, Abd El-Galil E. Amr, Seik Weng Ng and Edward R.

T. Tiekink

S1. Comment

Benzo- and naphthopyran-derivatives can possess biological and pharmacological activities, such as anti-coagulant, spasmolytic, diuretic, anti-cancer and anti-anaphylactin activities (Bonsignore et al., 1993). Some of these compounds can also be employed as cosmetics, pigments and as potential biodegradable agrochemicals (Hafez, et al., 1987). Derivatives of 4H-pyran are also known to exhibit biological activities (El-Agrody et al., 2011; Sabry et al., 2011), and form the focus of on-going studies of their chemistry. In this connection, herein, the crystal and molecular structure of the title compound, (I), is described.

In (I), Fig. 1, the 14 non-hydrogen atoms of the 1H-benzo[f]chromene fused-ring system are co-planar with a r.m.s. deviation of the fitted atoms = 0.052 Å. The maximum deviations are 0.136 (2) Å for the methine-C11 atom and -0.052 (2) Å for the aromatic-C7 atom. This implies that the furan ring is approximately planar as borne out by the observation that the methine-C11 atom lies only 0.132 (2) Å above the plane of the remaining atoms (r.m.s. deviation = 0.0107 Å), indicating a flattened half-chair conformation. The fluorobenzene ring is approximately perpendicular to the 1H

-benzo[f]chromene residue, forming a dihedral angle of 85.30 (7)°. The methoxy group is co-planar with the ring to which it is attached as seen in the value of the C14—O2—C6—C5 torsion angle of 0.5 (3)°. The structure described here resembles very closely those of the 4-bromo (Wang et al., 2008) and 2-CF3 (Shekhar et al., 2012) derivatives of the

parent compound, as well as that of the 7-methoxy analogue (Amr et al., 2013).

Hydrogen bonding features in the crystal packing whereby 12-membered {···HNC3N}2 synthons formed by

centrosymmetrically related molecules arise from the formation of amine-NH···N(cyano) hydrogen bonds, Table 1. These are connected into a three-dimensional architecture by CH···N2(cyano), C—H···π and ππ [inter-centroid distance for (O1,C1,C10–C13)···(C4–C9)i = 3.6671 (10) Å, inter-planar angle = 4.19 (8)° for i: 1 - x, 1 - y, 1 - z]

interactions, Fig. 2 and Table 1. The second amine-H2 atom does not participate in a significant intermolecular interaction.

S2. Experimental

A solution of 6-bromo-2-naphthol (0.01 mol) in EtOH (30 ml) was treated with α-cyano-p-fluorocinnamonitrile (0.01 mol) and piperidine (0.5 ml). The reaction mixture was heated until complete precipitation occurred corresponding to a reaction time of 60 min. The solid product which formed was collected by filtration and recrystallized from ethanol to give the title compound, (I), in the form of light brown prisms; M.pt: 529–530 K.

S3. Refinement

The C-bound H atoms were geometrically placed (C–H = 0.93–0.98 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

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[image:4.610.123.487.67.349.2]

Figure 1

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[image:5.610.135.475.72.521.2]

Acta Cryst. (2013). E69, o476–o477

Figure 2

A view in projection down the b axis of the crystal packing in (I). The N—H···N, C—H···N, C—H···π and ππ

interactions are shown as blue, orange, purple and brown dashed lines, respectively.

3-Amino-1-(4-fluorophenyl)-8-methoxy-1H-benzo[f]chromene-2-carbonitrile

Crystal data

C21H15FN2O2

Mr = 346.35

Triclinic, P1 Hall symbol: -P 1

a = 8.9672 (7) Å

b = 10.4365 (8) Å

c = 10.9058 (8) Å

α = 103.063 (7)°

β = 106.859 (7)°

γ = 111.399 (8)°

V = 844.01 (11) Å3

Z = 2

F(000) = 360

Dx = 1.363 Mg m−3

Mo radiation, λ = 0.71073 Å Cell parameters from 2078 reflections

θ = 3.2–27.5°

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Prism, light-brown

Data collection

Agilent SuperNova Dual

diffractometer with an Atlas detector Radiation source: SuperNova (Mo) X-ray

Source

Mirror monochromator

Detector resolution: 10.4041 pixels mm-1

ω scan

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)

Tmin = 0.722, Tmax = 1.000

7109 measured reflections 3902 independent reflections 2716 reflections with I > 2σ(I)

Rint = 0.023

θmax = 27.6°, θmin = 3.2°

h = −11→11

k = −13→12

l = −14→13

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 > 2σ(F2)] = 0.049

wR(F2) = 0.138

S = 1.05 3902 reflections 244 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2(F

o2) + (0.0568P)2 + 0.1033P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.20 e Å−3

Δρmin = −0.16 e Å−3

Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4

Extinction coefficient: 0.031 (4)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,

conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used

only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2

are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq

F1 0.65107 (18) 1.02622 (15) 1.19074 (13) 0.0888 (4) O1 0.93475 (14) 0.70759 (13) 0.65915 (12) 0.0489 (3) O2 0.08769 (17) 0.77609 (16) 0.33736 (14) 0.0685 (4) N1 1.0769 (2) 0.62403 (19) 0.79544 (18) 0.0538 (4) N2 0.8096 (2) 0.4809 (2) 0.97164 (18) 0.0655 (5) C1 0.7901 (2) 0.72705 (17) 0.59527 (16) 0.0416 (4) C2 0.8067 (2) 0.7931 (2) 0.49837 (18) 0.0511 (4)

H2A 0.9069 0.8184 0.4806 0.061*

C3 0.6756 (2) 0.8201 (2) 0.43063 (18) 0.0518 (4)

H3 0.6879 0.8664 0.3681 0.062*

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Acta Cryst. (2013). E69, o476–o477

H5 0.3935 0.8522 0.3199 0.059*

C6 0.2310 (2) 0.75979 (19) 0.40231 (17) 0.0493 (4) C7 0.2135 (2) 0.6892 (2) 0.49622 (17) 0.0503 (4)

H7 0.1100 0.6585 0.5094 0.060*

C8 0.3452 (2) 0.66482 (18) 0.56843 (16) 0.0444 (4)

H8 0.3307 0.6182 0.6305 0.053*

C9 0.50492 (19) 0.70961 (16) 0.55037 (15) 0.0391 (4) C10 0.64573 (19) 0.68629 (16) 0.62547 (15) 0.0370 (3) C11 0.63936 (18) 0.62664 (16) 0.73856 (15) 0.0370 (3)

H11 0.5315 0.5327 0.7006 0.044*

C12 0.79503 (19) 0.59719 (16) 0.78873 (15) 0.0396 (4) C13 0.93049 (19) 0.63973 (17) 0.75081 (16) 0.0411 (4) C14 0.0952 (3) 0.8443 (3) 0.2389 (2) 0.0773 (6) H14A −0.0123 0.8498 0.2013 0.116*

H14B 0.1107 0.7867 0.1661 0.116*

H14C 0.1921 0.9424 0.2829 0.116*

C15 0.63823 (18) 0.73347 (16) 0.85967 (15) 0.0376 (3) C16 0.7538 (2) 0.88289 (19) 0.91135 (18) 0.0509 (4)

H16 0.8299 0.9174 0.8704 0.061*

C17 0.7591 (3) 0.9820 (2) 1.0222 (2) 0.0614 (5)

H17 0.8370 1.0825 1.0558 0.074*

C18 0.6474 (2) 0.9291 (2) 1.08140 (18) 0.0567 (5) C19 0.5336 (2) 0.7830 (2) 1.03607 (19) 0.0614 (5)

H19 0.4600 0.7495 1.0792 0.074*

C20 0.5293 (2) 0.6848 (2) 0.92405 (17) 0.0507 (4)

H20 0.4517 0.5844 0.8918 0.061*

C21 0.80450 (19) 0.53183 (18) 0.88874 (17) 0.0453 (4) H1 1.096 (3) 0.588 (2) 0.861 (2) 0.065 (6)* H2 1.158 (3) 0.672 (2) 0.772 (2) 0.063 (6)*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

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C12 0.0442 (8) 0.0377 (8) 0.0383 (8) 0.0195 (6) 0.0159 (6) 0.0168 (7) C13 0.0443 (8) 0.0390 (8) 0.0399 (8) 0.0205 (7) 0.0150 (7) 0.0156 (7) C14 0.0899 (15) 0.0878 (16) 0.0666 (13) 0.0557 (13) 0.0184 (11) 0.0427 (12) C15 0.0386 (8) 0.0412 (8) 0.0351 (8) 0.0187 (6) 0.0145 (6) 0.0181 (6) C16 0.0589 (10) 0.0453 (10) 0.0502 (10) 0.0188 (8) 0.0305 (8) 0.0192 (8) C17 0.0745 (12) 0.0440 (10) 0.0576 (11) 0.0199 (9) 0.0313 (10) 0.0123 (9) C18 0.0660 (11) 0.0633 (12) 0.0422 (9) 0.0335 (9) 0.0254 (8) 0.0117 (9) C19 0.0593 (11) 0.0734 (13) 0.0491 (10) 0.0220 (9) 0.0328 (9) 0.0195 (9) C20 0.0501 (9) 0.0492 (10) 0.0450 (9) 0.0129 (7) 0.0224 (7) 0.0172 (8) C21 0.0399 (8) 0.0488 (9) 0.0491 (9) 0.0212 (7) 0.0159 (7) 0.0234 (8)

Geometric parameters (Å, º)

F1—C18 1.362 (2) C8—C9 1.423 (2)

O1—C13 1.3508 (19) C8—H8 0.9300

O1—C1 1.3933 (18) C9—C10 1.428 (2)

O2—C6 1.3665 (19) C10—C11 1.508 (2)

O2—C14 1.419 (2) C11—C12 1.513 (2)

N1—C13 1.345 (2) C11—C15 1.529 (2)

N1—H1 0.89 (2) C11—H11 0.9800

N1—H2 0.87 (2) C12—C13 1.351 (2)

N2—C21 1.146 (2) C12—C21 1.410 (2)

C1—C10 1.369 (2) C14—H14A 0.9600

C1—C2 1.400 (2) C14—H14B 0.9600

C2—C3 1.356 (2) C14—H14C 0.9600

C2—H2A 0.9300 C15—C20 1.379 (2)

C3—C4 1.416 (2) C15—C16 1.381 (2)

C3—H3 0.9300 C16—C17 1.379 (2)

C4—C9 1.415 (2) C16—H16 0.9300

C4—C5 1.418 (2) C17—C18 1.363 (3)

C5—C6 1.364 (2) C17—H17 0.9300

C5—H5 0.9300 C18—C19 1.357 (3)

C6—C7 1.402 (2) C19—C20 1.387 (2)

C7—C8 1.361 (2) C19—H19 0.9300

C7—H7 0.9300 C20—H20 0.9300

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Acta Cryst. (2013). E69, o476–o477

C2—C3—C4 120.94 (16) O2—C14—H14A 109.5

C2—C3—H3 119.5 O2—C14—H14B 109.5

C4—C3—H3 119.5 H14A—C14—H14B 109.5

C9—C4—C5 120.25 (15) O2—C14—H14C 109.5 C9—C4—C3 118.64 (15) H14A—C14—H14C 109.5 C5—C4—C3 121.11 (16) H14B—C14—H14C 109.5 C6—C5—C4 120.17 (16) C20—C15—C16 118.03 (15) C6—C5—H5 119.9 C20—C15—C11 121.98 (14) C4—C5—H5 119.9 C16—C15—C11 119.93 (13) O2—C6—C5 125.58 (17) C17—C16—C15 121.56 (16) O2—C6—C7 114.43 (15) C17—C16—H16 119.2 C5—C6—C7 119.99 (15) C15—C16—H16 119.2 C8—C7—C6 121.13 (16) C18—C17—C16 118.34 (17)

C8—C7—H7 119.4 C18—C17—H17 120.8

C6—C7—H7 119.4 C16—C17—H17 120.8

C7—C8—C9 120.94 (16) C19—C18—F1 118.80 (17) C7—C8—H8 119.5 C19—C18—C17 122.38 (16)

C9—C8—H8 119.5 F1—C18—C17 118.82 (17)

C4—C9—C10 120.40 (14) C18—C19—C20 118.59 (16) C4—C9—C8 117.51 (14) C18—C19—H19 120.7 C10—C9—C8 122.09 (15) C20—C19—H19 120.7 C1—C10—C9 117.30 (14) C15—C20—C19 121.09 (16) C1—C10—C11 121.40 (14) C15—C20—H20 119.5 C9—C10—C11 121.23 (13) C19—C20—H20 119.5 C10—C11—C12 109.72 (12) N2—C21—C12 177.89 (18)

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C2—C1—C10—C9 1.8 (2) C16—C17—C18—F1 −179.78 (17) O1—C1—C10—C11 4.4 (2) F1—C18—C19—C20 179.49 (17) C2—C1—C10—C11 −175.07 (14) C17—C18—C19—C20 −1.1 (3) C4—C9—C10—C1 −2.9 (2) C16—C15—C20—C19 1.0 (3) C8—C9—C10—C1 176.87 (14) C11—C15—C20—C19 178.28 (16) C4—C9—C10—C11 174.03 (13) C18—C19—C20—C15 0.2 (3)

Hydrogen-bond geometry (Å, º)

Cg1 is the centroid of the C1–C4,C9,C10 ring.

D—H···A D—H H···A D···A D—H···A

N1—H1···N2i 0.89 (2) 2.16 (2) 3.043 (2) 170.0 (18)

C19—H19···N2ii 0.93 2.51 3.259 (3) 138

C11—H11···Cg1iii 0.98 2.90 3.7084 (17) 141

C14—H14C···Cg1iv 0.96 2.92 3.772 (3) 148

Figure

Table 1
Figure 1
Figure 2

References

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